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    • 6. 发明申请
    • CHIRAL LIGANDS
    • WO2010055112A1
    • 2010-05-20
    • PCT/EP2009/065082
    • 2009-11-13
    • SOLVIAS AGPUGIN, BenoîtWYSS, Adrian
    • PUGIN, BenoîtWYSS, Adrian
    • C07F17/02C07B31/00C07B53/00
    • C07F17/02
    • Process for preparing ligands of the formula (1), in which R 1 is C 1 -C 8 -alkyl, unsubstituted cyclopentyl, cyclohexyl, norbornyl or adamantyl, or cyclopentyl or cyclohexyl, substituted by 1 to 3 C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy, or benzyl, phenyl, naphthyl and anthryl which are unsubstituted or substituted by 1 to 3 C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -fluoroalkyl or C 1 -C 4 -fluoroalkoxy, F and Cl, each of R 2 and R 3 is independently a C-bonded hydrocarbon radical or a heterohydrocarbon radical, and R 4 is C 1 -C 4 -alkyl, cyclopentyl, cyclohexyl, phenyl, methylphenyl, methylbenzyl or benzyl, which comprises (a) stereoselective metallation in ortho position to the amine side-chain of a compound of formula (A) in which R 4 is as defined above, reaction with a dihalide of formula R 1 -PX2 in which R 1 is as defined above and X is Cl or Br, stereoselective hydrolysis to give a compound containing an SPO group, and reaction with a secondary phosphine of formula H-PR 2 R 3 in which R 2 and R 3 are as defined above, to give the compounds of formula (1). New ligands obtained by that process and metal complexes thereof.
    • 制备式(1)配体的方法,其中R 1是被1至3个C 1 -C 4 - 烷基或C 1 -C 4 - 烷基取代的C 1 -C 8 - 烷基,未被取代的环戊基,环己基,降冰片基或金刚烷基或环戊基或环己基, 烷氧基或苄基,未被取代或被1至3个C 1 -C 4 - 烷基,C 1 -C 4 - 烷氧基,C 1 -C 4 - 氟代烷基或C 1 -C 4 - 氟烷氧基,F和Cl各自取代的苯基,萘基和蒽基,每个R 2 并且R 3独立地是C键合的烃基或杂烃基,R 4是C 1 -C 4 - 烷基,环戊基,环己基,苯基,甲基苯基,甲基苄基或苄基,其包括(a)在邻近位置的立体选择性金属化 - 其中R 4如上定义的式(A)化合物与式R1-PX2的二卤化物反应,其中R 1如上定义,X​​是Cl或Br,立体选择性水解,得到含有SPO的化合物 并与其中R2和R3如上定义的式H-PR2R3的次膦反应 得到式(1)的化合物。 通过该方法获得的新配体及其金属络合物。